CN109119180A - Conductive material, electrode plate and electrochemical energy storage device - Google Patents
Conductive material, electrode plate and electrochemical energy storage device Download PDFInfo
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- CN109119180A CN109119180A CN201710481134.3A CN201710481134A CN109119180A CN 109119180 A CN109119180 A CN 109119180A CN 201710481134 A CN201710481134 A CN 201710481134A CN 109119180 A CN109119180 A CN 109119180A
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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Abstract
The application provides a conductive material, an electrode plate and an electrochemical energy storage device. The conductive material comprises a conductive material matrix and a coating layer. The coating layer is coated on the surface of the conductive material matrix and comprises a conductive polymer. The conductive polymer is selected from a complex of polythiophene and polyanion. The conductive polymer has an obvious PTC effect, can provide effective field protection for an electrochemical energy storage device when the electrochemical energy storage device is abused, improves the thermal shock performance and the overcharge performance of the electrochemical energy storage device, namely improves the safety performance of the electrochemical energy storage device, and simultaneously enables the electrochemical energy storage device to have good high-temperature storage performance, cycle performance and rate capability.
Description
Technical field
This application involves energy storage device field more particularly to a kind of conductive materials, electrode slice and electrochemical energy storage device.
Background technique
Operating voltage is high, specific capacity is big, self discharge is small, has extended cycle life, memory-less effect, ring because having for lithium ion battery
The advantages that border is friendly has been captured rapidly consumer electronics product market and has sharply been expanded in the application of power energy storage field.
However, thermal runaway caused by the safety problem of lithium ion battery, especially lithium ion battery abuse has become lithium-ion electric
One of maximum hidden danger in the application process of pond.During abuse, the violent heat production of lithium ion battery, the heat meeting that can not be dispersed in time
Cause the serious accumulation of heat of inside lithium ion cell, eventually leads to lithium ion battery thermal runaway.
Research staff generallys use addition flame-retardant additive, using ceramic isolation film and with temperature sensitivity at present
The technological means such as collector improve the security performance of lithium ion battery.In these technological means, some can improve lithium from
The dynamic performance of lithium ion battery is deteriorated while sub- battery safety, some are then to the security performance of lithium ion battery
Improvement is ideal not enough.The safety problem of lithium ion battery is still urgently to be resolved, especially in inside lithium ion cell heat
Before acutely generating, inhibit the side reaction of inside lithium ion cell, this is extremely important to the security performance for improving lithium ion battery.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of conductive material, electrode slice and electricity
Chemical energy storage device, the conducting polymer have apparent PTC effect, can be electrification in electrochemical energy storage device abuse
It learns energy storage device and effective scene protection is provided, improve the thermal shock resistance properties and over-charging of electrochemical energy storage device, that is, improve
The security performance of electrochemical energy storage device, while electrochemical energy storage device being made to have both good high-temperature storage performance, cycle performance
And high rate performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of conductive materials comprising conductive
Material matrix and clad.The clad is coated on the surface of the conductive material substrates and including conducting polymer.Institute
State the complex that conducting polymer is selected from polythiophene and polyanion.
In the another aspect of the application, this application provides a kind of electrode slices comprising the conduction material of the application one side
Material.
At the another aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application another party
The electrode slice in face.
Compared with the existing technology, the application has the beneficial effect that
The conducting polymer of the application has apparent PTC effect, can be electrification in electrochemical energy storage device abuse
It learns energy storage device and effective scene protection is provided, improve the thermal shock resistance properties and over-charging of electrochemical energy storage device, that is, improve
The security performance of electrochemical energy storage device, while electrochemical energy storage device being made to have both good high-temperature storage performance, cycle performance
And high rate performance.
Specific embodiment
The following detailed description of conductive material according to the application and preparation method thereof, electrode slice and electrochemical energy storage device.
Illustrate the conductive material according to the application first aspect first.
Conductive material according to the application first aspect includes conductive material substrates and clad.The clad cladding
The conductive material substrates surface and including conducting polymer.The conducting polymer is selected from polythiophene and polyanion
Complex.
In the conductive material according to the application first aspect, formed by the complex of polythiophene and polyanion
Conducting polymer has apparent positive temperature coefficient effect, i.e. PTC effect, conductivity shows excellent when temperature is relatively low
It is different, the normal use of conductive material substrates and electrochemical energy storage device is not influenced；When temperature is increased to conductivity transition temperature
(Curie-point temperature) nearby when, due to segment twisting and the conductivity of the complex of dedoping effect polythiophene and polyanion
Can sharply it decline.Therefore when electrochemical energy storage device occur thermal shock, overcharge, short-circuit failure when, the temperature of electrochemical energy storage device
Degree steeply rises and (would generally rise to 100 DEG C or more), after reaching the conductivity transition temperature of conducting polymer, clad
The complex of polythiophene and polyanion can be changed into electronic isolation from electronic state is led due to segment twisting and dedoping effect
State is led electronic capability and is sharply declined, and so as to limit the transmission of electronics, cuts off the electronics of electrochemical energy storage device internal-response
Source provides the overheating protection at scene for electrochemical energy storage device, improves the thermal shock resistance properties of electrochemical energy storage device and overcharging property
Can, while cycle performance, high-temperature storage performance and the high rate performance of electrochemical energy storage device can also be improved to a certain extent.
In the conductive material according to the application first aspect, the conductivity transition temperature of the conducting polymer is
80 DEG C~150 DEG C, if conductivity transition temperature is too low, electrochemical energy storage device stops work in the case where slightly heating up
Make, can seriously limit the application of electrochemical energy storage device and influences usage experience, conversely, if conductivity transition temperature is excessively high,
Electrolyte when high temperature in electrochemical energy storage device has been enough to be pyrolyzed, at this time anode and cathode active materials almost thermal runaway, electrification
Whether the internal-response electron source for learning energy storage device, which is cut off, does not have any meaning to the security performance of electrochemical energy storage device
Justice.
In the conductive material according to the application first aspect, the conductive material substrates are selected from zero dimension conduction material
One or more of material, one-dimensional electric material, two-dimentional conductive material, three-dimensional conductive material.
In the conductive material according to the application first aspect, the partial size D50 of the zero dimension conductive material be 5nm~
100nm；The partial size D50 of the one-dimensional electric material is 1nm~100nm；It is described two dimension conductive material partial size D50 be 1 μm~
10μm；The partial size D50 of the three-dimensional conductive material is 3 μm~80 μm.
In the conductive material according to the application first aspect, the zero dimension conductive material is selected from acetylene black, conduction
One or more of carbon black (Super P, Super S, 350G, SP-Li), Ketjen black (EC300J, ECP, EC-600JD)；Institute
It states one-dimensional electric material and is selected from one or more of carbon nanotube (CNT), carbon fiber (VGCF), carbon nanocoils；The two dimension
Conductive material is selected from one or more of graphene, carbon nanobelts；The three-dimensional conductive material be selected from electrically conductive graphite (KS-6,
One or more of SFG-6).
In the conductive material according to the application first aspect, the conducting polymer is selected from formula 1, formula 2,3 institute of formula
One or more of compound shown；In formula 1, formula 2, formula 3, m, y, q be 5~500 integer；N, x, p are integer and take
Value range is respectively the 1/10~1/3 of m, y, q；R11、R12、R13、R14、R21、R22、R23、R24、R31、R32、R33、R34It is respectively independent
Ground be selected from H, F, Cl, Br, I, nitro, sulfonic group, substituted or unsubstituted carbon atom number be 1~10 alkyl, replace or not
One of the alkynes base that alkylene that substituted carbon atom number is 2~10, substituted or unsubstituted carbon atom number are 2~10,
Wherein, alkyl, alkylene, alkynes base can also be replaced by one or more of halogen atom, N atom, O atom, S atom；
R15、R25、R35It is each independently selected from alkyl, the substituted or unsubstituted carbon that substituted or unsubstituted carbon atom number is 1~10
One of alkynes base that alkylene that atomicity is 2~10, substituted or unsubstituted carbon atom number are 2~10, sulfonyl,
In, alkyl, alkylene, alkynes base can also be replaced by one or more of halogen atom, N atom, O atom, S atom.
In the conductive material according to the application first aspect, in formula 1, formula 2, formula 3, the value of m, y, q are excessive,
It will affect the cycle performance of electrochemical energy storage device, the value of m, y, q are too small, and the complex of polythiophene and polyanion can be into one
Step polymerization release H2, influence the high-temperature storage performance of electrochemical energy storage device.
In the conductive material according to the application first aspect, specifically, the conducting polymer is selected from followingization
Close one or more of object；But the application is without being limited thereto.
In the conductive material according to the application first aspect, the quality of the conducting polymer is the conduction material
The 1%~40% of gross mass is expected, when the quality of conducting polymer is too small, it is impossible to which reaching improves electrochemical energy storage device safety
The effect of performance, when the quality of conducting polymer is too big, passivation conducting material matrix is reduced electrification by excessive conducting polymer
Learn the cycle performance and high rate performance of energy storage device.It is understood that in range defined herein, electrochemical energy storage
Thermal shock resistance properties, over-charging, cycle performance, high-temperature storage performance and the high rate performance of device can be improved, if super
The range out, corresponding performance will necessarily be affected, but require relatively low or more secondary use to need for some
It, equally can a degree of thermal shock resistance properties for improving electrochemical energy storage equipment, excessively punching performance, cycle performance, high temperature in asking
Storage performance and high rate performance.
In the conductive material according to the application first aspect, the thickness of the clad is less than or equal to 5 μm, works as packet
When coating is excessively thin, it is impossible to have the function that improve electrochemical energy storage device security performance, it is excessive conductive when clad is too thick
Passivation conducting material matrix is reduced the cycle performance and high rate performance of electrochemical energy storage device by polymer.Preferably, the packet
Coating with a thickness of 0.001 μm~5 μm.
Secondly illustrate the preparation method of the conductive material according to the application second aspect.
The conduction material of the application first aspect is used to prepare according to the preparation method of the conductive material of the application second aspect
Material, comprising steps of in deionized water by conducting polymer dissolution, once being stirred, being stirring evenly and then adding into conductive material
Matrix carries out secondary agitation, carries out vacuum spray drying after stirring, can be obtained conductive material substrates surface coated with conductive
The conductive material of polymer.
In the preparation method of the conductive material according to the application second aspect, the time of the secondary agitation is 1h
~10h, mixing time is too short, and conducting polymer is unable to fully and is uniformly coated on the surface of conductive material substrates, when stirring
Between it is too long, then unnecessary working hour is lost, it is preferable that the time of the secondary agitation be 4h~7h.
In the preparation method of the conductive material according to the application second aspect, the temperature of the vacuum spray drying
It is 20 DEG C~90 DEG C, it is preferable that the temperature of the vacuum spray drying is 40 DEG C~70 DEG C.
Illustrate the electrode slice according to the application third aspect again.
Electrode slice according to the application third aspect includes the conductive material according to the application first aspect.
In the electrode slice according to the application third aspect, the electrode slice includes collector and active material
Layer.The active material layer includes active material and conductive material.The conductive material is described in the application first aspect
Conductive material.
In the electrode slice according to the application third aspect, the quality of the conductive material is the active material layer
The additional amount of the 0.1%~20% of gross mass, conductive material is too small, then the ability of the conductive son of electrode slice is poor, influences electrochemistry storage
The dynamic performance of energy device, the additional amount of conductive material is excessive, because its own polarization is small, relative potentials height and specific surface area
Big active site is more, increases so producing the side reactions such as gas, unfavorable to the security performance of electrochemical energy storage device.It is understood that
It is that in range defined herein, thermal shock resistance properties, over-charging, cycle performance, the height of electrochemical energy storage device are gentle
Storage performance and high rate performance can be improved, if exceeding the range, corresponding performance will necessarily be affected, but right
It is required in relatively low or more secondary use demand in some, a degree of can equally improve electrochemical energy storage equipment
Thermal shock resistance properties crosses punching performance, cycle performance, high-temperature storage performance and high rate performance.
In the electrode slice according to the application third aspect, the preparation method of electrode slice does not have special requirement, presses
More solito preparation.
Finally illustrate the electrochemical energy storage device according to the application fourth aspect.
Electrochemical energy storage device according to the application fourth aspect includes the electrode slice according to the application third aspect.
In the electrochemical energy storage device according to the application fourth aspect, the electrochemical energy storage device includes anode
Piece, negative electrode tab, isolation film and pack case etc..According to electrode slice described in the application third aspect either electrochemical energy storage
The positive plate of device is also possible to negative electrode tab.In embodiments herein, electrode described in the application third aspect is only shown
Piece is the embodiment of the positive plate of electrochemical energy storage device, but the application is without being limited thereto.
In the electrochemical energy storage device according to the application fourth aspect, it should be noted that the electrochemistry storage
Energy device can be lithium ion battery, sodium-ion battery, lithium metal battery or supercapacitor.In embodiments herein, only
The embodiment that electrochemical energy storage device is lithium ion battery is shown, but the application is without being limited thereto.
In lithium ion battery, positive electrode active materials can be selected from LiFePO4、LiCoO2、LiaNixCoyM(1-x-y)O2、
LiNixMn1-xO2、LiNiO2、LiMnO2、Li2MnO4、LiV3O8One or more of, wherein M be selected from Mn, Al, Zr, Ti, V,
One or more of Mg, Fe, B, 0.95≤a≤1.2, x, y, x+y are respectively less than 1.
In lithium ion battery, negative electrode active material can be selected from the micro- carbon of lithium metal, natural graphite, artificial graphite, interphase
One or more of ball, hard carbon, soft carbon, silicon, silicon alloy, silico-carbo compound, tin and kamash alloy.
In lithium ion battery, the electrolyte can be liquid electrolyte, and the electrolyte may include lithium salts and organic
Solvent.
In lithium ion battery, the specific type of the lithium salts is unrestricted.Specifically, the lithium salts can be selected from hexafluoro phosphorus
Sour lithium (LiPF6), bis trifluoromethyl sulfimide lithium (LiTFSI), trifluoromethyl sulfonic acid lithium (LiTFS), double fluorine sulfimide lithiums
(LiFSI), difluoro di-oxalate lithium borate (LiDFOB), di-oxalate lithium borate (LiBOB), difluorophosphate (LiPO2F2), difluoro
One or more of double oxalic acid lithium phosphates (LiDFOP), tetrafluoro oxalic acid lithium phosphate.
In lithium ion battery, the specific type of the organic solvent is not particularly limited, can be according to actual needs
It is selected.Preferably, using non-aqueous organic solvent.The non-aqueous organic solvent may include the carbonic ester of any kind, carboxylic acid
Ester.Carbonic ester may include cyclic carbonate or linear carbonate.The non-aqueous organic solvent may also include the halogenated of carbonic ester
Compound.Specifically, the organic solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene carbonate, carbonic acid Asia
Pentyl ester, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate, γ-Ding Nei
One or more of ester, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs.Tool
Body, the isolation film can be selected from the MULTILAYER COMPOSITE of polyethylene film, polypropylene screen, polyvinylidene fluoride film and above-mentioned membrane material
Film, but the application is not limited only to these.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery is only shown in embodiment, but is applied
It is without being limited thereto.In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available
It obtains.
Embodiment 1
(1) preparation of positive plate
In deionized water by the dissolution of conductive polymer compounds 2, it is stirring evenly and then adding into conductive material substrates conductive carbon
Black Super P (partial size D50 is 30nm), is stirred for 5 hours, then the vacuum spray drying at 50 DEG C, obtains compound 2 and coat
Super P, i.e. acquisition conductive material, wherein the additional amount of conductive polymer compounds 2 is conductive material gross mass
20%, clad with a thickness of 8nm.
By positive electrode active materials LiNi0.6Co0.2Mn0.2O2, binder polyvinylidene fluoride (PVDF), above-mentioned conductive material
It is sufficiently mixed in mass ratio for 96.5:1.5:2 with Solvents N-methyl -2-Pyrrolidone (NMP), obtains positive slurry after mixing evenly
Anode sizing agent, is then uniformly coated on the plus plate current-collecting body aluminium foil with a thickness of 12 μm, toasts 1h at 110 DEG C by material, it
Positive plate successively is obtained through overcompaction, cutting afterwards.
(2) preparation of negative electrode tab
By negative electrode active material graphite, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber (SBR), cathode
Conductive material conductive black Super P 96.5:1:1:1.5 in mass ratio is sufficiently mixed with solvent deionized water, after mixing evenly
Negative electrode slurry is obtained, then negative electrode slurry is uniformly coated on the negative current collector copper foil with a thickness of 8 μm, at 110 DEG C
1h is toasted, successively obtains negative electrode tab through overcompaction, cutting later.
(3) preparation of electrolyte
It is in drying shed, ethylene carbonate (EC), methyl ethyl carbonate (EMC) is mixed for EC:EMC=30:70 in mass ratio
It closes, lithium salts LiPF is added later6, electrolyte is obtained after mixing, wherein LiPF6Concentration be 1mol/L.
(4) preparation of isolation film
Using polyethylene film (PE) as isolation film.
(5) preparation of lithium ion battery
Positive plate, negative electrode tab, isolation film are separated to and are wound the naked battery core of squarely, soldering polar ear fills naked battery core
Enter in package foil aluminum plastic film, then at 80 DEG C baking water removal after, inject corresponding electrolyte and seal, later through standing,
The processes such as hot cold pressing, chemical conversion, shaping, volume test, obtain lithium ion battery.
Embodiment 2
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
The additional amount of conductive polymer compounds 2 is the 1% of conductive material gross mass,
Clad with a thickness of 1nm.
Embodiment 3
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
The additional amount of conductive polymer compounds 2 is the 40% of conductive material gross mass,
Clad with a thickness of 25nm.
Embodiment 4
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Positive electrode active materials LiNi0.6Co0.2Mn0.2O2, binder polyvinylidene fluoride (PVDF), conductive material quality
Than for 98.4:1.5:0.1.
Embodiment 5
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Positive electrode active materials LiNi0.6Co0.2Mn0.2O2, binder polyvinylidene fluoride (PVDF), conductive material quality
Than for 78.5:1.5:20.
Embodiment 6
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive material substrates conductive carbon black Super P (partial size D50 is 30nm) is replaced with into electrically conductive graphite KS-6 (partial size
D50 be 3.4 μm), clad with a thickness of 1nm.
Embodiment 7
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive material substrates conductive carbon black Super P (partial size D50 is 30nm) is replaced with into electrically conductive graphite KS-6 (partial size
D50 is 3.4 μm) with the mixture of conductive carbon black Super P (partial size D50 be 30nm), and the mass ratio of the two is 1:1.
Embodiment 8
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 1.
Embodiment 9
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 3.
Embodiment 10
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 4.
Embodiment 11
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 5.
Embodiment 12
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 6.
Embodiment 13
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive polymer compounds 2 are replaced with into compound 7.
Comparative example 1
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Using the conductive carbon black Super P of uncoated conducting polymer, (partial size D50 does conductive material for 30nm).
Comparative example 2
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
Conductive material is done using conductive polymer compounds 2.
Comparative example 3
With embodiment 1, difference is the preparation process of lithium ion battery,
(1) preparation of positive plate
By positive electrode active materials LiNi0.6Co0.2Mn0.2O2, binder polyvinylidene fluoride (PVDF), conducting polymer materialization
Close object 2, conductive carbon black Super P (partial size D50 is 30nm) is 97:1.5:0.4:1.6 and Solvents N-methyl -2- pyrrole in mass ratio
Pyrrolidone (NMP) is sufficiently mixed, and obtains anode sizing agent after mixing evenly, then anode sizing agent is uniformly coated to a thickness of 12
μm plus plate current-collecting body aluminium foil on, 1h is toasted at 110 DEG C, later successively through overcompaction, cutting obtain positive plate.
The parameter of table 1 embodiment 1-13 and comparative example 1-3
The test process of lithium ion battery will be illustrated next.
(1) the thermal shock security performance test of lithium ion battery
At 25 DEG C, lithium ion battery is charged to voltage with 1C constant current as 4.2V, being charged to electric current later with 4.2V constant pressure is
Then lithium ion battery is put into insulating box by 0.05C, with the heating rate of 5 DEG C/min by insulating box be warming up to 200 DEG C and
200 DEG C are kept for 2 hours, the time needed for thermal runaway occurs in lithium ion battery during this are recorded, with the temperature-rise period out-of-service time
Lithium ion battery thermal shock security performance can be characterized.
(2) overcharge safety of lithium ion battery can be tested
At 25 DEG C, lithium ion battery is charged to voltage with 1C constant current as 4.2V, being charged to electric current later with 4.2V constant pressure is
0.05C, then it is 1.5U with 1C constant-current charge to voltage that lithium ion battery, which is 100%SOC, at this time, required time record
For t (s).
Lithium ion battery reaches SOC (%)=t/3600 × 100% when 1.5U.
(3) the cycle performance test of lithium ion battery
At 25 DEG C, lithium ion battery is charged to voltage with 1C constant current as 4.2V, being charged to electric current later with 4.2V constant pressure is
Then 0.05C is 2.8V with 1C constant-current discharge to voltage, the above are a charge and discharge cycles processes, records lithium ion battery
Then lithium ion battery is carried out 500 charge and discharge cycles according to above-mentioned condition by discharge capacity for the first time, record the 500th circulation
Discharge capacity.
25 DEG C of lithium ion battery circulation 500 times after capacity retention ratio (%)=(the 500th time circulation discharge capacity/head
Secondary discharge capacity) × 100%.
(4) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, the initial discharge capacity of lithium ion battery is denoted as C0, then by the lithium ion battery completely filled 60
Storage (voltage being charged to as 4.2V with 1C constant current, then it is 0.05C that 4.2V constant pressure, which is charged to electric current) in DEG C environment, after storage is 30 days full
It takes out, tests its discharge capacity and be denoted as C30。
60 DEG C of lithium ion battery storage 30 days after capacity retention ratio (%)=(C30/C0) × 100%.
(5) the high rate performance test of lithium ion battery
At 25 DEG C, lithium ion battery is charged to voltage with 1C constant current as 4.2V, being charged to electric current later with 4.2V constant pressure is
Then 0.05C with 0.5C, 3C constant-current discharge to voltage is respectively 2.8V, stands 5 minutes after electric discharge every time, record lithium-ion electric
The discharge capacity in pond is respectively C0.5C、C3C.Wherein, it is calculate by the following formula to obtain electric discharge appearance of the lithium ion battery under different multiplying
Amount ratio.
High rate performance (%)=C of lithium ion battery 3C/0.5C3C/C0.5C× 100%.
The performance test results of table 2 embodiment 1-13 and comparative example 1-3
It is analyzed by the data in table 2 it is found that in embodiment 1-13 and comparative example 1-3, the conductive material of the application is not
Under the premise of influencing cycle performance of lithium ion battery, high-temperature storage performance and high rate performance, it can effectively extend lithium-ion electric
Pond temperature-rise period out-of-service time, and reduce SOC when lithium ion battery reaches 1.5U, to the thermal shock resistance properties of lithium ion battery and
Over-charging has clear improvement.
Analysis is it is found that conducting polymer content is small (embodiment 2) in embodiment 1-3 and comparative example 1-3, lithium ion battery
Thermal shock resistance properties and over-charging improvement it is relatively small, and conducting polymer content is big (embodiment 3), lithium ion battery
Thermal shock resistance properties and over-charging improvement it is obvious, but the cycle performance of lithium ion battery and the certain journey of high-temperature storage performance
It is affected to degree, nevertheless, above-mentioned two situations, which remain unchanged, can play the temperature-rise period failure for extending lithium ion battery
SOC when time, reduction lithium ion battery arrival 1.5U, while improving circulation volume conservation rate, high temperature storage capacity retention ratio
With the effect of 3C/0.5C high rate performance；When conducting polymer content is moderate, the thermal shock resistance properties of lithium ion battery and overcharging property
It can improve obviously, combine cycle performance, high-temperature storage performance and the high rate performance of lithium ion battery；In comparative example 2 with
For conducting polymer as conductive material, conductive capability is limited, thus cycle performance of lithium ion battery, high-temperature storage performance and again
Rate performance is poor；Conducting polymer and conductive carbon black Super P are simply mixed and are introduced into anode sizing agent in comparative example 3, due to
Conducting polymer can not effectively influence the ducting capacity of electronics at high temperature, so changing to the security performance of lithium ion battery
Kind effect is unobvious.
The analysis in embodiment 1, embodiment 4-5 is it is found that when using identical conductive material in positive plate, in positive plate
The additive amount of conductive material is to the cycle performance of lithium ion battery, high-temperature storage performance, high rate performance, thermal shock resistance properties and overcharges
The improvement of performance has an impact.In positive plate when the additive amount of conductive material less (embodiment 4), conductive effect is limited, to lithium from
Cycle performance and high-temperature storage performance when the normal use of sub- battery have an impact, and the additive amount of conductive material is more in positive plate
When (embodiment 5), a large amount of conductive material provides more active sites, the influence lithium ion battery that this can be different degrees of
Security performance and dynamic performance；When the additive amount of conductive material in positive plate is moderate (embodiment 2), the heat of lithium ion battery
Impact property and over-charging improve obviously, while following for lithium ion battery has also been taken into account under the premise of not influencing high rate performance
Ring performance and high-temperature storage performance.
Analysis is it is found that although different conducting polymer and conductive material substrates are to lithium ion battery in embodiment 6-13
Chemical property, the improvement of security performance and high rate performance it is different.For example, in the conducting polymer of embodiment 8, m
Value is small, and the complex of polythiophene and polyanion can further polymerize release H2, influence the high temperature storage of lithium ion battery
Energy and high rate performance.And correspondingly, in conducting polymer, when m, y, q value are moderate, n, x, p value are larger, polythiophene and poly-
The doping effect of the complex of anion is good, then bigger to the thermal shock resistance properties of lithium ion battery and over-charging improvement amplitude,
To cycle performance, high-temperature storage performance and high rate performance good compatibility.
In embodiment 6 and embodiment 7, when using electrically conductive graphite KS-6 as conductive material substrates, good conductivity, but its
Grain is larger, and the site for causing conductive material to contact with each other with positive electrode active materials is few, to improvement surface of positive electrode active material and just
The effect of electric conductivity between the active material particle of pole is limited, therefore the polarization of lithium ion battery can be made to increase to a certain extent
Greatly, to influence the high rate performance of lithium ion battery.And use the mixing of partial size lesser Super P and the biggish KS-6 of partial size
Object is conductive material, can greatly improve the electric conductivity between surface of positive electrode active material and positive electrode active materials particle, is guaranteed
Lithium ion battery takes into account good security performance, cycle performance and high temperature storage under the premise of with preferable high rate performance
Performance.
It follows that conductive material provided by the present application can greatly improve lithium ion battery after being applied to lithium ion battery
Thermal shock resistance properties and over-charging, improve the security performance of lithium ion battery, while lithium ion battery can also be made to take into account circulation
Performance, high-temperature storage performance and high rate performance.
Further, since conductive material incorporation way in positive and negative plate is similar with the mechanism of action, comparative example and implementation here
Its influence to performance of lithium ion battery is only described in detail with the positive plate containing conductive material in example.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to this
Some modifications and changes of application should also be as falling into the protection scope of claims hereof.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, not to the application constitute any restrictions.
Claims (11)
1. a kind of conductive material characterized by comprising
Conductive material substrates；And
Clad, is coated on the surface of the conductive material substrates and including conducting polymer, and the conducting polymer is selected from poly-
The complex of thiophene and polyanion.
2. conductive material according to claim 1, which is characterized in that the conductivity transition temperature of the conducting polymer is
80 DEG C~150 DEG C.
3. conductive material according to claim 1, which is characterized in that the conductive material substrates are selected from zero dimension conduction material
One or more of material, one-dimensional electric material, two-dimentional conductive material, three-dimensional conductive material.
4. conductive material according to claim 3, which is characterized in that
The partial size D50 of the zero dimension conductive material is 5nm~100nm；
The partial size D50 of the one-dimensional electric material is 1nm~100nm；
The partial size D50 of the two dimension conductive material is 1 μm~10 μm；
The partial size D50 of the three-dimensional conductive material is 3 μm~80 μm.
5. conductive material according to claim 3, which is characterized in that
The zero dimension conductive material is selected from one or more of acetylene black, conductive black, Ketjen black；
The one-dimensional electric material is selected from one or more of carbon nanotube, carbon fiber, carbon nanocoils；
The two dimension conductive material is selected from one or more of graphene, carbon nanobelts；
The three-dimensional conductive material is selected from electrically conductive graphite.
6. conductive material according to claim 1, which is characterized in that the conducting polymer is selected from formula 1, formula 2,3 institute of formula
One or more of compound shown；
In formula 1, formula 2, formula 3,
M, the integer that y, q are 5~500；
N, x, p are integer and value range is respectively the 1/10~1/3 of m, y, q；
R11、R12、R13、R14、R21、R22、R23、R24、R31、R32、R33、R34It is each independently selected from H, F, Cl, Br, I, nitro, sulphur
The alkene that alkyl that acidic group, substituted or unsubstituted carbon atom number are 1~10, substituted or unsubstituted carbon atom number are 2~10
One of alkyl, alkynes base that substituted or unsubstituted carbon atom number is 2~10, wherein alkyl, alkylene, alkynes base
It can also be replaced by one or more of halogen atom, N atom, O atom, S atom；
R15、R25、R35It is each independently selected from the alkyl, substituted or unsubstituted that substituted or unsubstituted carbon atom number is 1~10
Carbon atom number be 2~10 alkylene, substituted or unsubstituted carbon atom number be 2~10 alkynes base, one in sulfonyl
Kind, wherein alkyl, alkylene, alkynes base can also be taken by one or more of halogen atom, N atom, O atom, S atom
Generation.
7. conductive material according to claim 6, which is characterized in that the conducting polymer is in following compounds
It is one or more of；
8. conductive material according to claim 1, which is characterized in that the quality of the conducting polymer is the conduction material
Expect the 1%~40% of gross mass.
9. conductive material according to claim 1, which is characterized in that the thickness of the clad is less than or equal to 5 μm, preferably
Ground, the clad with a thickness of 0.001 μm~5 μm.
10. a kind of electrode slice, which is characterized in that including conductive material according to claim 1 to 9.
11. a kind of electrochemical energy storage device, which is characterized in that including electrode slice according to claim 10.
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| CN112467314A (en) * | 2020-11-03 | 2021-03-09 | 东莞市创明电池技术有限公司 | Thermosensitive material, electrode and preparation method thereof, and lithium secondary battery |
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